MXPA00003520A - Processes for making a granular detergent composition containing mid-chain branched surfactants - Google Patents
Processes for making a granular detergent composition containing mid-chain branched surfactantsInfo
- Publication number
- MXPA00003520A MXPA00003520A MXPA/A/2000/003520A MXPA00003520A MXPA00003520A MX PA00003520 A MXPA00003520 A MX PA00003520A MX PA00003520 A MXPA00003520 A MX PA00003520A MX PA00003520 A MXPA00003520 A MX PA00003520A
- Authority
- MX
- Mexico
- Prior art keywords
- integer
- detergent
- surfactant
- alkyl
- chain
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 195
- 239000000203 mixture Substances 0.000 title claims abstract description 191
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 168
- 238000000034 method Methods 0.000 title claims abstract description 82
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 90
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 73
- 239000004615 ingredient Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000001694 spray drying Methods 0.000 claims abstract description 16
- -1 polyhydroxy portions Chemical class 0.000 claims description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 46
- 239000008187 granular material Substances 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003945 anionic surfactant Substances 0.000 claims description 16
- 239000001187 sodium carbonate Substances 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- JNYAEWCLZODPBN-CTQIIAAMSA-N Sorbitan Chemical class OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229920000223 polyglycerol Polymers 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 7
- 150000004760 silicates Chemical class 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 6
- 230000002209 hydrophobic Effects 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical class OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-L CHEBI:8154 Chemical class [O-]P([O-])=O ABLZXFCXXLZCGV-UHFFFAOYSA-L 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002314 glycerols Chemical class 0.000 claims description 4
- 150000002462 imidazolines Chemical class 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 150000003890 succinate salts Chemical class 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 230000003472 neutralizing Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-M isethionate Chemical class OCCS([O-])(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-M 0.000 claims 3
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 37
- 150000008051 alkyl sulfates Chemical class 0.000 abstract description 35
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 39
- 238000005054 agglomeration Methods 0.000 description 24
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 24
- 230000002776 aggregation Effects 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 16
- 150000001298 alcohols Chemical class 0.000 description 14
- 238000005342 ion exchange Methods 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 10
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 238000007046 ethoxylation reaction Methods 0.000 description 8
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 8
- 238000000280 densification Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000005670 sulfation reaction Methods 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004429 atoms Chemical group 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 240000007170 Cocos nucifera Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000011031 large scale production Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- VQOIVBPFDDLTSX-UHFFFAOYSA-M sodium;3-dodecylbenzenesulfonate Chemical class [Na+].CCCCCCCCCCCCC1=CC=CC(S([O-])(=O)=O)=C1 VQOIVBPFDDLTSX-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- GHNRTXCRBJQVGN-UHFFFAOYSA-N 4-dodecan-6-ylbenzenesulfonic acid Chemical compound CCCCCCC(CCCCC)C1=CC=C(S(O)(=O)=O)C=C1 GHNRTXCRBJQVGN-UHFFFAOYSA-N 0.000 description 1
- MXNAGTAMQHQIBG-UHFFFAOYSA-M 8-methylpentadecyl sulfate Chemical compound CCCCCCCC(C)CCCCCCCOS([O-])(=O)=O MXNAGTAMQHQIBG-UHFFFAOYSA-M 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- WWKJSUQDMGKSIF-UHFFFAOYSA-M CC(C)CCCCCCCCCCCCCCCOS([O-])(=O)=O Chemical compound CC(C)CCCCCCCCCCCCCCCOS([O-])(=O)=O WWKJSUQDMGKSIF-UHFFFAOYSA-M 0.000 description 1
- MGIKOYWPIYJKAR-UHFFFAOYSA-M CCCCCCC(C)CCCCCCCCOS([O-])(=O)=O Chemical compound CCCCCCC(C)CCCCCCCCOS([O-])(=O)=O MGIKOYWPIYJKAR-UHFFFAOYSA-M 0.000 description 1
- YRBQGXUZYACFPW-UHFFFAOYSA-M CCCCCCCCC(C)CCCCCCOS([O-])(=O)=O Chemical compound CCCCCCCCC(C)CCCCCCOS([O-])(=O)=O YRBQGXUZYACFPW-UHFFFAOYSA-M 0.000 description 1
- IQOPFGOEBAYAFG-UHFFFAOYSA-M CCCCCCCCCC(C)CCCCCOS([O-])(=O)=O Chemical compound CCCCCCCCCC(C)CCCCCOS([O-])(=O)=O IQOPFGOEBAYAFG-UHFFFAOYSA-M 0.000 description 1
- FUAHKIOYTHTCFA-UHFFFAOYSA-M CCCCCCCCCCC(C)CCCCOS([O-])(=O)=O Chemical compound CCCCCCCCCCC(C)CCCCOS([O-])(=O)=O FUAHKIOYTHTCFA-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 102000033147 ERVK-25 Human genes 0.000 description 1
- 229920002456 HOTAIR Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N Oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229960003330 Pentetic Acid Drugs 0.000 description 1
- 108091005771 Peptidases Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 210000002374 Sebum Anatomy 0.000 description 1
- MYAJTCUQMQREFZ-UHFFFAOYSA-K TPPTS Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned Effects 0.000 description 1
- 230000003750 conditioning Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic Secondary and tertiary amines Drugs 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 102000004882 lipase Human genes 0.000 description 1
- 108090001060 lipase Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000019960 monoglycerides of fatty acid Nutrition 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003606 oligomerizing Effects 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N p-acetaminophenol Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003385 sodium Chemical group 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000003381 solubilizing Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical class [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Abstract
Processes for preparing high density detergent composition containing a mid-chain branched surfactant are provided. The processes involve spray drying, agglomerating, mixing, blending or a combination thereof and produce a granular and/or agglomerated detergent composition directly from mid-chain branched surfactants and other starting detergent ingredients. The mid-chain branched surfactants are mid-chain branched primary alkyl sulfate surfactants and mid-chain branched primary alkyl alkoxoxylated sulfate surfactants having an average of greather than 14.5 carbon atoms.
Description
PROCEDURES FOR ELABORATING A COMPOSITION OF GRANULATED DETERGENT CONTAINING AGENTS
BRANCHED SURFACTANTS IN THE MIDDLE REGION OF THE CHAIN
FIELD OF THE INVENTION
The present invention is generally defined as processes for producing a granular detergent composition. More particularly, the invention is directed to processes during which the detergent or agglomerate granules are produced from starting detergent materials, one of which is a branched surfactant in the middle region of the chain. The branched surfactants in the middle region of the chain are primary alkylsulphate surfactants branched in the middle region of the chain and branched primary alkoxylated alkylsulphate surfactants in the middle region of the chain that have an average of more than 14.5 carbon atoms. carbon. The process produces a free flowing granular detergent composition which can be sold commercially as a modern compact detergent product.
BACKGROUND OF THE INVENTION
Recently, there has been considerable interest within the detergent industry in laundry detergents that are "compact" and therefore have low dosage volumes. To facilitate the production of these so-called low dosage detergents, many attempts have been made to produce high volume density detergents, for example with a density of 600 g / l or greater. Low-dose detergents are currently in great demand because they conserve natural resources and can be sold in small packages which are more convenient for consumers. Generally speaking, there are two primary types of processes by which granules or detergent powders can be prepared. The first type of process involves the spray drying of an aqueous detergent suspension in a spray-drying tower to produce highly porous detergent granules. In the second type of process the various components of detergents are mixed dry after which they are agglomerated with a binder such as a nonionic or anionic surfactant. In both processes, the most important factors that govern the density of the resulting detergent granules are the density, porosity and surface area of the various starting materials and their respective chemical composition. There is an interest in the art to provide processes that increase the density of the detergent granules or powders. Particular attention has been given to the densification of spray dried granules by a post-tower treatment. For example, an attempt involves an intermittent procedure in which spray-dried detergent powders or granules containing sodium tripolyphosphate and sodium sulfate are densified and spheronized in a Marumerizer®. This apparatus comprises a substantially horizontal rough rotary table positioned inside and at the base of a cylinder with a substantially vertical smooth wall. This process, however, is essentially an intermittent process and is therefore less suitable for producing large-scale detergent powders. More recently, other methods have been developed to increase the density of "post tower" detergent granules or typically spray dried. Such procedures require a first apparatus, which pulverizes or grinds the granules, and a second apparatus which increases the density of the pulverized granules by agglomeration. These procedures achieve the desired increase in density by the treatment or densification of "post-tower" spray-dried granules. The technique is also filled with descriptions of procedures that impose the agglomeration of detergent compositions. For example, attempts have been made to agglomerate detergent builders by mixing zeolite and / or layered silicates in a mixer to form the free flowing agglomerates. furtherIt has been an established practice for detergent formulators to use surfactants and combinations thereof in detergent compositions. By way of example, various anionic surfactants are commonly used, especially alkylbenzene sulphonates, alkyl sulfates, alkylalkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates in detergent formulations. Surfactants have found use as detergent components that can remove a wide variety of soils and stains. However, detergent manufacturers make a consistent effort to improve the detersive properties of detergent compositions by providing new and improved surfactants. A problem commonly associated with anionic surfactants is their sensitivity to cold water and / or hard water. It has been difficult to obtain improved cleaning performance above and beyond current standards, especially for granular detergent compositions that are to be used under cold wash water and / or hard water conditions. Therefore, it would be desirable to have a process for making a detergent composition that exhibits improved cleaning performance through a wide variety of soils and stains. Accordingly, there still remains a need in the art for a process that produces a granular and / or agglomerated detergent composition from starting detergent ingredients that include a surfactant that exhibits improved cleaning performance over a wide variety of soils and spots. In addition, there is also a need for a process as such which is more efficient and economical to facilitate the large-scale production of low-dose or compact detergents.
TECHNICAL BACKGROUND
The following references are directed to the densification of spray-dried granules: Appel et al., Patent E.U.A. No. 5,133,924 (Lever); Bortolotti et al., Patent E.U.A. No. 5,160,657 (Lever); Johnson et al., British Patent No. 1, 517,713 (Unilever); and Curtis European Patent Application 451, 894. The following references are directed to the production of detergents by agglomeration: Beerse et al., Patent E.U.A. No. 5,108,646 (Procter &Gamble); Hollingsworth et al., European Patent Application No. 351, 937 (Unilever); Swatling et al, patent E.U.A. No. 5,205,958, and Capeci et al, patent E.U.A. No. 5,366,652 (Procter &Gamble). The E.U.A. 3,480,556 to deWitt, et al., Issued November 25, 1969; EP 439,316, published by Lever on July 31, 1991 and EP 684,300 published by Lever on November 29, 1995, describe beta-branched alkyl sulfates. EP 439,316, discloses certain laundry detergents containing a branched primary commercial C14 / C15 alkyl sulfate, called LIAL 145 sulfate. It is believed that the latter has 61% branching at position 2; 30% of the above involves branching with a hydrocarbon chain having four or more carbon atoms. The patent E.U.A. No. 3,480,556 describes mixtures of 10 to 90 parts of a straight chain primary alkylsulfate and 90 to 10 parts of a beta-branched primary alcohol sulfate (branched at position 2) of the formula R2-R1CH CH OSCOC
wherein the total number of carbon atoms varies from 12 to 20 and R1 is a straight chain alkyl radical containing from 9 to 17 carbon atoms and R2 is a straight chain alkyl radical containing from 1 to 9 carbon atoms (67% 2-methyl branching and 33% 2-ethyl branching are exemplified). As noted hereinabove, R.G. Laughlin in "The Aqueous Phase Behavior of Surfactants", Academic Press, N.Y. (1994) p. 347 describes the observation that as the branching moves away from the 2-alkyl position toward the center of the alkyl hydrophobe there is a decrease in Krafft temperatures. See also Finger et al., "Detergent alcohols - the effect of alcohol structure and molecular weight on surfactant properties", J. Amer. Oil Chemists' Society, Vol. 44, p. 525 (1967) and Technical Bulletin, Shell Chemical Co., SC: 364-80. EP 342,917 A, Unilever, published on November 23, 1989 discloses laundry detergents containing a surfactant system, in which the main anionic surfactant is an alkyl sulfate which has a "broad range" of chain lengths. of alkyl (the experimental part seems to involve the mixture of surfactants of coconut chain length and sebum). The patent of E.U.A. 4,102,823 and GB 1, 399,966 describe other laundry compositions containing conventional alkyl sulphates. The patent GB 1, 299,966, Matheson et al., Published on July 2, 1975, describes a detergent composition in which the surfactant system is constituted by a mixture of sodium tallow alkyl sulphate and nonionic surfactants. The methyl substituted sulfates include the known "isostearyl sulfates; these are typical mixtures of isomeric sulfates having a total of 18 carbon atoms. For example, EP 401, 462 A, assigned to Henkel, published on December 12, 1990, discloses certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulfates such as sodium isostearylsulfate. See also K.R. Wormuth and S. Zushma, Langmuir, Vol. 7, (1991), pp 2048-2053 (technical studies on a number of branched alkyl sulfates, especially the "branched Guerbet" type; R. Varadaraj et al., J. Phys. Chem ., Vol. 95, (1991), pp 1671-1676 (describing the surface tensions of a variety of surfactants of the "linear Guerbet" and "branched Guerbet" class including alkyl sulfates); Varadaraj et al., J. Colloid and Interface Sci., Vol. 140, (1990), pp. 31-34 (referring to foam formation data for surfactants including C12 and C13 alkyl sulphates containing 3 and 4 branches of methyl, respectively); and Varadaraj et al., Langmuir, Vol. 6 (1990), pp 1376-1378 (which describes the micropolarity of aqueous micellar solutions of surfactants including branched alkyl sulphates).
The "Guerbet linear" alcohols are available from Henkel, for example EUTANOL G-16. The primary alkyl sulphates derived from alcohols made by Oxo reaction on oligomers of propylene or n-butylene are described in the patent of E.U.A. No. 5,245,072 assigned to Mobil Corp. See also the patent of E.U.A. 5,284,989, assigned to Mobil Oil Corp. (a method for producing substantially linear hydrocarbons by oligomerization of a lower oleofin at elevated temperatures with intermediate and restricted pore siliceous zeolite acid), and U.S. Patents. 5,026,933 and 4,870,038, both from Mobil Oil Corp. (a process for producing substantially linear hydrocarbons by oligomerizing a lower oleofin at elevated temperatures with ZSM-23 siliceous acid zeolite). See also: Surfactant Science Series, Marcel Dekker, N.Y. (various volumes including those entitled "Anionic Surfactants" and "Surfactant Biodegradation", the last of RD Swisher, second edition, published in 1987 as volume 18, see especially pages 20-24 of "Hidrophobic groups and their sources"; pp 28 -29 from "Alcohols", pp 34-35 of "Primary Alkil Sulfates" and pp 35-36 of "Secondary Alkil Sulfates"); and the literature on "higher" alcohols or "detergents" from which alkyl sulphates are typically made, including: CEH's market research report "Detergent Alcohols" by R.F. Modler et al., Chemical Economics Handbook, 1993, 609.5000-609.5002; Kirk Othmer's Encyclopedia of Chemical Technology, 4th ed. Wiley, N.Y. 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 and references cited therein.
BRIEF DESCRIPTION OF THE INVENTION
The present invention meets the aforementioned needs in the art by providing a process which produces a granular and / or agglomerated detergent composition directly from branched surfactants in the middle region of the chain and from other starting detergent ingredients. The methods include a variety of modalities including spray drying, agglomeration, mixing, blending, and combinations thereof. The branched surfactants in the middle region of the chain are primary alkylsulphate surfactants branched in the middle region of the chain and branched primary alkoxylated alkylsulphate surfactants in the middle region of the chain that have an average of more than 14.5 carbon atoms. carbon. The detergent compositions resulting from the processes of the invention exhibit improved cleaning performance through a wide variety of stains and / or soils, even under relatively high water hardness and low temperature wash water conditions. As used in the present invention, the term "agglomerates" refers to particles formed by agglomeration by accumulation of the starting ingredients (particles) which typically have an average particle size smaller than that of the agglomerates formed. All percentages and ratios used in the present invention are expressed as percentages by weight (dry basis) unless otherwise indicated. All documents are incorporated in the present invention for reference. All viscosities referred to in the present invention are measured at 70 ° C (± 5 ° C) and shear rates of about 10 to 100 s "1. In accordance with one aspect of the invention, it is provided A process for preparing a crisp, high-flux, free-flowing detergent composition The method comprises the steps of: A method for continuously preparing a high-density detergent composition comprising the steps of: (A) continuously mixing a surfactant paste Detergent and dry starting detergent material in a high-speed mixer / densifier to obtain detergent agglomerates, wherein the ratio of the surfactant paste to dry detergent material is from about 1: 10 to about 10: 1, the surfactant paste containing branched surfactant compounds in the middle region of the chain of the formula: Ab-XB wherein a) Ab is a branched alkyl portion in the middle region of the chain, hydrophobic from 9 to 22 total carbons in the portion, preferably from about C12 to about C18, having: 1) a chain Longest linear carbon bound to the -XB portion in the range of 8 to 21 carbon atoms; 2) one or more C1-C3 alkyl portions branching from this longest linear carbon chain; 3) at least one of the branching alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon 2 position range, counting from the # 1 carbon that joins the -XB portion to the carbon position -2, the terminal carbon minus 2 carbons; and 4) the surfactant composition has an average total number of carbon atoms in the Ab-X portion in the above formula within the range of more than 14.5 to about 18, preferably from about 15 to about 17; b) B is a hydrophilic portion chosen from sulfates, sulphonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, glycerol phosphate sulfonate esters, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinatamines, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, setionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulphates, diglycolamides, diglycolamide sulphates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycerol ethers, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkenes sulfonates, amidopropyl betaines , alkylated quaternary compounds, alkylated / polyhydroxyalkylated quaternary compounds, alkylated quaternary compounds, alkylated / polyhydroxylated oxopropyl quaternary compounds, imidazolines, 2-yl succinates, alkyl esters sulfonated cos and sulfonated fatty acids; and c) X is -CH2-. B) mixing the detergent agglomerates in a mixer / densifier to further densify and agglomerate the detergent agglomerates; and (C) drying the detergent agglomerates so that the high density detergent composition is formed. Another aspect of the invention involves similar steps, in which step (A) requires continuously mixing an acid precursor of an anionic surfactant and drying the starting detergent material containing an alkaline inorganic material capable of neutralizing the acid precursor in a mixer / high speed densifier to obtain detergent agglomerates. In another aspect of the invention, a method involving spray drying and agglomeration of detergent ingredients is provided to provide a high density detergent composition. More particularly, this method comprises the steps of: (A) spray drying an aqueous suspension containing a branched surfactant in the middle region of the chain and adjunct detergent ingredients to form spray-dried granules, in which the branched surfactant in the middle region of the chain has the formula, as described above; (B) continuously mixing a detergent surfactant paste and the dry starting detergent material in a high speed mixer / densifier to obtain detergent agglomerates, wherein the ratio of the surfactant paste to the dry detergent material is from about 1: 10 to about 10: 1; (C) mixing the detergent agglomerates in a moderate speed mixer / densifier to further densify and agglomerate the detergent agglomerates; and (D) combining the granules and the detergent agglomerates so that the high density detergent composition is formed. Accordingly, it is an object of the present invention to provide a process for producing an agglomerated and / or granulated detergent composition directly from starting detergent ingredients that includes a surfactant having improved cleaning performance. It is also an object of the invention to provide a process as such that is not limited by unnecessary process parameters so that large scale production of low or compact dose detergents is more economical and efficient. These and other objects, features and present advantages of the invention will be apparent to those skilled in the art from the reading of the following drawings, detailed description of the preferred embodiments and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a flowchart showing a preferred process in which two agglomeration mixers / densifiers, a fluidized bed drying oven, a fluidized bed cooler and a screen apparatus according to a process according to the invention are placed in series. the invention.
DETAILED DESCRIPTION OF THE PREFERRED MODALITY
The present process is used in the production of detergent compositions by means of the agglomeration of starting detergent ingredients which include a branched surfactant in the middle region of the chain or by spray drying techniques which may include further processing of the detergent granules "after the tower". With the term "post-tower" detergent granules, it refers to those detergent granules that have been processed through a spray-drying tower or similar apparatus.
Agglomeration process Reference is now made to Figure 1 which presents a flow chart illustrating the agglomeration process and various modalities thereof. In the first step of the process, the invention imposes continuously mixing in a high-speed mixer / densifier 10 various streams of starting detergent ingredients including a flow of surfactant paste 12 which includes the branched surfactant in the middle region of the chain and a dry starting detergent material stream 14. Based on the basis weight of the finished agglomerate, the surfactant paste 12 preferably comprises water and from about 25% to about 75%, preferably from about 35% to about 65%, and more preferred from about 38% to about 55% of the branched surfactant in the middle region of the chain or combinations of surfactant as such and of adjunctive surfactants, all of which are described in detail hereinafter in the present invention. Preferably, the dry starting detergent material 14 comprises from about 10% to about 50%, more preferred from about 15% to about 45% and, even more preferred, from about 20% to about 40% of a builder based of aluminosilicate or zeolite and from about 10% to about 40%, preferably from about 15% to about 30%, and, more preferably, from about 15% to about 25% of a sodium carbonate. It should be understood that additional starting detergent ingredients of which several are described hereinbelow may be mixed in a high speed mixer / densifier 10 without departing from the scope of the invention. However, it has been discovered that the surfactant paste 12 and the dry starting detergent material 14 are continuously mixed within the ratio ranges described herein so as to ensure the production of the crisp high density detergent composition, of free flow. Preferably, the ratio of surfactant paste 12 to dry starting detergent material 14 is from about 1: 10 to about 10: 1, more preferred from about 1: 4 to about 4: 1 and, even more preferred, about 2 : 1 to approximately 2: 3. Furthermore, it has also been discovered that the first process step can be successfully completed, under the processing parameters described herein, in a high-speed mixer / densifier 10 which is preferably a Lódige CB mixer or a branded mixer. Similary. These types of mixers essentially consist of an empty, horizontal static cylinder having a pivoting shaft mounted centrally around which several plow-shaped blades are attached. Preferably, the arrow rotates at a speed of about 300 rpm to about 2500 rpm, more preferred from about 400 rpm to about 1600 rpm. Preferably, the average residence time of the detergent ingredients in the high speed mixer / densifier 10 is preferably in the range of from about 2 seconds to about 45 seconds, and more preferably from about 5 seconds to about 15 seconds. The average residence time can be measured conveniently and accurately by dividing the drop weight of the mixer / densifier between production (eg kg / hr). The resulting detergent agglomerates formed in the high speed mixer / densifier 10 are then fed to a low or moderate speed mixer / densifier 16 in which further agglomeration and densification is performed. This particular moderate speed mixer / densifier 16 used in the method of the present invention should include liquid distribution and agglomeration tools so that both techniques can be performed simultaneously. It is preferred that the moderate speed mixer / densifier 16 be, for example, a Lódige KM mixer (Ploughshare), a Drais® K-T 160 mixer or a similar brand mixer. The speed of the centrally rotating main shaft is from about 30 to about 160 rpm, preferably from about 50 to about 100 rpm. The average residence time in the moderate speed mixer / densifier 16 is preferably from about 0.25 minutes to about 15 minutes, more preferred the residence time is from about 0.5 to about 10 minutes. This average residence time can also be measured conveniently and accurately by dividing the drop weight of the mixer / densifier into a constant state between production (eg kg / hr). The liquid distribution is achieved with cutters, generally smaller in size than the rotating shaft, which preferably operate at approximately 3600 rpm. In accordance with the present method, the high-speed mixer / densifier 10 and the combined moderate-speed mixer / densifier 16 preferably impart a required amount of energy to form the desired agglomerates. More particularly, the method of the present invention imparts from about 5 x 1010 erg / kg to about 2 x 1012 erg / kg at a rate of about 3 x 108 erg / kg-sec to about 3 x 109 erg / kg-sec for form the high density detergent agglomerates with free flow. The power supply and the feed rate can be determined by calculations from energy readings for the moderate speed mixer / densifier with and without granules, the residence time of the granules in the mixer / densifier, and the mass of the granules in the mixer / densifier. Such calculations are clearly within the skill of the art. The density of the resulting detergent agglomerates leaving the moderate speed mixer / densifier is at least 600 g / l, more preferred from about 700 g / l to about 800 g / l. After that, the detergent agglomerates are dried in a fluidized bed drying oven 18 or similar apparatus to obtain the high density granular detergent composition that is ready to be packaged and sold as a compact, low dose detergent at this point . The particle porosity of the resulting detergent agglomerate in the composition is preferably in the range of about 5% to about 20%, more preferably about 10%. As will be appreciated by those skilled in the art, a low porosity detergent agglomerate provides a low or dense detergent product, towards which the present procedure is mainly directed. In addition, one attribute of dense or densified detergent agglomerates is the relative particle size. The present process typically provides agglomerates having an average particle size from about 400 microns to about 700 microns, and more preferred from about 475 microns to about 600 microns. As used herein, the phrase "average particle size" refers to individual agglomerates and not to individual particles or detergent granules. The aforementioned combination of porosity and particle size results in agglomerates having density values of 600 g / l and greater. Such a feature is especially useful in the production of low dose laundry detergents as well as other granular compositions such as dishwasher compositions.
Optional process steps In an optional step of the present process, the detergent agglomerates exiting the fluidized bed drying furnace 18 are then conditioned by cooling the agglomerates in a fluidized bed cooler or similar apparatus as is well known in the art. . Another optional process step involves adding a coating agent to improve the flow characteristic and / or minimizing over-agglomeration of the detergent composition in one or more of the following locations of the present process: (1) the coating agent can be adding directly after the fluidized bed cooler 20 as shown by means of the flow of coating agent 22 (preferred); (2) the coating agent can be added between the fluidized bed drying oven 18 and the fluidized bed cooler 20 as shown by the flow of coating agent 24; (3) the coating agent can be added between the fluidized bed drying oven 18 and the moderate speed mixer / densifier 16 as shown by the flow 26; and / or (4) the coating agent can be added directly to the moderate speed mixer / densifier 16 and to the fluidized bed drying furnace 18 as shown by the flow 28. It should be understood that the coating agent can be added in any of one or a combination of streams 22, 24, 26 and 28 as shown in Figure 1. The flow of coating agent 22 is most preferred in the process of the present invention. See Capeci et al, patent E.U.A. 5,516,448, issued May 14, 1996 and Capeci et al, patent E.U.A. 5,489,392, issued February 6, 1996. The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent may also be the improved builder material described in more detail hereinafter. However, the coating agent can be one or more combinations of builder material, aluminosilicates, carbonates, silicates and the like. The coating agent not only increases the free-flowing character of the resulting detergent composition which is desirable by consumers since it allows for easy dosing of the product by bucket during use, but also serves to control agglomeration by avoiding or leading to minimum over-agglomeration, especially when added directly to the moderate speed mixer / densifier 16. As is well known to those skilled in the art, over-agglomeration can lead to very undesirable flow properties and aesthetic aspects in the final detergent product. Optionally, the method comprises the step of sprinkling an additional binder on one or both of the mixers / densifiers 10 and 16. A binder is added for the purpose of increasing the agglomeration by supplying a "binder" or "tackifier" agent for the binder. detergent components. The binder of preference is selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinylpyrrolidone, polyacrylates, citric acid and mixtures thereof. Other suitable binding materials including those listed in the present invention are described in Beerse et al, U.S. Pat. No. 5,108,646 (Procter &Gamble Co.), the disclosure of which is incorporated herein by reference. Other optional steps contemplated by the present method include screening the larger sized detergent agglomerates in a screening apparatus 30 which can take a variety of forms including, but not limited to, conventional screens chosen for the desired particle size of the finished detergent product . Other optional steps include the conditioning of the detergent agglomerates by subjecting the agglomerates to further drying. Another optional step of the present method entails finishing the resulting detergent agglomerates by a variety of methods including spraying and / or mixing other conventional detergent ingredients, collectively referred to as finishing step 32 in Figure 1. For example, the finishing step comprises sprinkling perfumes, brighteners and enzymes on the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are known in the art. Preferably, the resulting detergent agglomerates produced by the process embodiments described herein contain from about 20% to about 50% by weight of the branched surfactant in the middle region of the chain, from about 10% to about 65% of a detergent builder such as aluminosilicate, and optionally, up to about 40% by weight of sodium carbonate. The levels of surfactant, builder and carbonate may vary beyond those given herein as described previously and later in the present invention.
Spray drying process One or more spray drying techniques can be used individually, or in combination with the aforementioned agglomeration processes, to make detergent compositions containing the branched surfactants in the middle region of the chain according to the invention. present invention. One or more spray-drying towers can be used to make granular laundry detergents that often have a density of about 500 g / L or less. In this process, an aqueous suspension of various heat-stable ingredients in the final detergent composition is configured as homogeneous granules by passing it through a spray-drying tower, using conventional techniques, at temperatures from about 175 ° C to about 225 ° C. . If spray drying is used as part of the general procedure in the present invention, the additional process steps as described herein may optionally be used to obtain the density level (ie,> 650 g / l) required by the low-dose, compact detergent products. For example, spray-dried granules from a tower can be further densified by charging a liquid such as water or a nonionic surfactant into the pores of the granules and / or by subjecting them to one or more high-speed mixers / densifiers. A high-speed mixer / densifier suitable for this process is the above-mentioned "CB 30" or "CB Recycler Lódige" which comprises a static cylindrical drum that has a rotating central shaft with mixing / cutting blades mounted on the same In use, the ingredients for a detergent composition are introduced into the drum and the arrow / blade assembly is rotated at speeds in the range of 100-2500 rpm to provide complete mixing / densification. See Jacobs et al, patent E.U.A. 5,149,455, issued September 22, 1992. Other such devices include devices sold under the trade name "Shugi Granulator" and under the trademark "Drais K-TTP 80. Another process step that can be used to further densify Spray-dried granules involve the grinding and agglomeration or deformation of the spray-dried granules in a moderate speed mixer / densifier so that particles having a lower porosity are obtained.The equipment of mixers / densifiers such as those mentioned above " Lódige KM "(Series 300 or 600) or" Lódige Ploughshare "are appropriate for this procedural step.Other useful equipment includes the device that can be obtained under the trade name" Drais KT 160. "This procedure step uses a mixer / moderate speed densifier (eg Lódige KM) can be used by itself or sequentially with the mixer / densifier high speed mentioned above (e. g. Lódige CB) to achieve the desired density. Other types of apparatuses for the manufacture of granules useful in the present invention include the apparatuses described in the patent E.U.A. 2,306,898, to G. L. Heller, December 29, 1942. While it might be more appropriate to use the high speed mixer / densifier followed by the low speed mixer / densifier, the sequential reverse mixer / densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times in the mixers / densifiers, operating temperatures of the equipment, temperature and / or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used for optimizing the densification of the spray-dried granules in the process of the invention. As an example, see the procedures in Appel et al, patent E.U.A. 5,133,924, issued July 28, 1992 (spray-dried granules are brought to a deformable state before densification); Delwel et al, patent E.U.A. 4,637,891, issued January 20, 1987 (granulation of spray-dried granules with a liquid binder and aluminosilicate); Kruse et al, patent E.U.A. 4,726,908, issued February 23, 1988 (granulation of spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, patent E.U.A. 5,160,657, issued November 3, 1992 (coating of densified spray dried granules with a liquid binder and aluminosilicate).
Blending Procedures Specifically, other aspects of the process of the invention include mixing the builder material with spray-dried granules, agglomerates or combinations thereof. This mixing step can be increased by combining the granules, agglomerates or combinations thereof with the builder material and a liquid binder as previously described in a mixing drum or other similar device. Optionally, the builder material may be coated with a nonionic surfactant or other liquid binder as previously described before the mixing step so as to avoid any harmful interaction with the other detergent ingredients (eg, anionic surfactants) ) before immersion in the wash solution (ie during processing and storage). This liquid binder coating (e.g., nonionic surfactant) also improves the flow properties of the detergent composition in which the builder material is included.
Other Processes Even another embodiment of the process, the high-density detergent composition can be produced by feeding an acidic precursor of an anionic surfactant, such as the branched surfactant in the middle region of the chain described in the present invention, an alkaline inorganic material (for example sodium carbonate) and optionally other detergent ingredients in a high speed mixer / densifier (residence time 5-30 sec.) so that agglomerates are formed which contain a partially or fully neutralized anionic surfactant salt and the Other ingredients of starting detergents. Next, the contents in the high-speed mixer / densifier can be sent to a moderate speed mixer / disinfector (eg, Lódige KM) for further agglomeration which results in the finished high-density detergent composition. In another process embodiment, the surfactant paste is premixed or extruded into a mixing apparatus or extruder apparatus such as a twinworm extruder (e.g., Werner and Pfleiderer, Continua Series) to structure the pulp for easier agglomeration. Additionally, structuring agents such as polymers, sodium hydroxide, sodium chloride, potassium hydroxide, silicates and the like can be used to make the paste more suitable so that larger amounts of surfactant can be loaded. See Aouad et al, patent E.U.A. No. 5,451, 354, issued September 19, 1995. Optionally, high density detergent compositions can be produced by mixing conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (eg, a ratio of 60:40 by weight). from granules to agglomerates) produced by one or a combination of the processes discussed in the present invention. Additional adjunct ingredients such as enzymes, perfumes, brighteners and the like may be sprinkled or mixed with the agglomerates, granules or mixtures thereof produced by the methods discussed in the present invention. Another method of the invention involves cooling a molten surfactant paste containing the branched surfactant in the middle region of the chain and forming flakes on a cooling roller, after which the flakes are milled to the desired particle size. The chilled flakes can be further dried using a rotating drum drying machine.
Surfactant Paste The viscoelastic surfactant paste used herein has viscoelastic fluid properties that can be described by a commonly used mathematical model that explains the shear thinning nature of the pulp. The mathematical model is called the Exponent Law Model and is described by the following relationship: s = K? N where s = shear stress (dynes / cm2), K = Consistency (Po¡se-secp "1),? = Shear rate (sec" 1), and n = velocity index (without dimension). The velocity index n varies from 0 to 1. The closer n is to O, the greater the shear thinning of the fluid. The closer it is n to 1, the closer it will be to simple Newtonian behavior, ie constant viscosity behavior. K can be interpreted as the apparent viscosity at a shear rate of 1 sec "1. In this context, the viscoelastic surfactant paste used in the process has a consistency K at 70 ° C and about 50,000 about 250,000 cPoise-sec "1 (500 to 2,500 Poise-sec" "1), most preferably from about 100,000 to about 195,000 cPoise-sec" "1 (1, 000 to 1, 950 Poise-sec" 1), and most preferably from about 120,000 to approximately 180,000 cPoise-secn "1 (1, 200 to 1, 800 Poise-sec" "1). Preferably, the surfactant paste has a shear rate n of from about 0.5 to about 0.25, most preferably from about 0.08 to about 0.20 and still most preferably from about 0.10 to about 0.15. The surfactant paste includes mixtures of surfactants comprising branched surfactant compounds in the middle region of their chain as described above in the present invention. In such compositions, certain branching points (eg, localization along the chain of the portions R, R ^ and / or R2 in the above formula) are preferred over other branch points along the structure of base of the surfactant. The following formula illustrates the branching interval in the middle region of the chain (ie, where the branching points occur), the branching interval in the middle region of the preferred chain and the branching interval
in the middle region of the chain that is especially preferred for branched mono-methyl alkyl AD portions useful in accordance with the present invention.
CH3CH2CH2CH2CH2CH2 (CH2) 1-7CH2CH2CH2CH2CH2-
I I I iinntteerrvvaalloo mmás more prreeffeerriiddoo I preferred interval branching interval "in the middle region of the chain
It should be noted that for substituted mono-methyl surfactants these ranges exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -X-B group.
The following formula illustrates the branching interval in the middle region of the chain, the branching interval in the middle region of the chain that is preferred and the branching interval in the middle region of the chain.
the chain which is especially preferred for di-methyl substituted alkyl A ^ portions useful in accordance with the present invention.
CH3CH2CH2CH2CH2CH2 (CH2)? - 6CH2CH2CH2CH2CH2-
in a reg a n d a ca tion Branched surfactant compositions which are preferred and useful in cleaning compositions in accordance with the present invention are described in greater detail hereinafter.
(1) Branched primary alkylsulfate surfactants in the middle region of its chain The branched surfactant compositions of the present invention may comprise two or more branched primary alkyl sulfate surfactants in the middle region of its chain having the formula
R R1 R2 I I I
CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zOS03M
The surfactant mixtures of the present invention comprise molecules having a linear primary alkyl sulfate chain base structure (ie, the longest linear carbon chain that includes the sulfated carbon atom). These base structures of the alkyl chain comprise from 12 to 19 carbon atoms; and in addition the molecules comprise a branched primary alkyl portion having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions in the range of greater than 14.5 to about 17.5. Thus, the blends of the present invention comprise at least one primary branched alkyl sulfate surfactant compound having a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the The total number of carbon atoms including the branching must be at least 14, and furthermore the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 17.5. For example, a primary total carbon alkylsulfate surfactant of 16 total carbon atoms having 13 carbon atoms in the base structure must have 1, 2 or 3 branching units (ie, R, R1 and / or R3) whereby the The total number of carbon atoms in the molecule is at least 16. In this example, the requirement of 16 total carbons can be satisfied in the same way by having, for example, a propyl branching unit or three methyl branching units . R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, most preferably hydrogen or methyl, and most preferably methyl), provided that R, R ^ and R2 do not be all hydrogen. Also, when z is 1, at least R or R1 is not hydrogen. Although for the purposes of the surfactant compositions of the present invention the above formula does not include molecules in which the units R, R ^ and R ^ are all hydrogen (i.e., unbranched linear primary alkyl sulphates), it should be recognized that the The compositions of the present invention may still further comprise a certain amount of unbranched linear primary alkyl sulfate. further, this non-branched linear primary alkyl sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the one or more branched primary alkyl sulfate surfactants in the middle region of its chain required in accordance with the present invention. invention, or for the purposes of formulating detergent compositions, a certain amount of unbranched linear primary alkyl sulphate can be mixed into the final product formulation. Furthermore, it should be similarly recognized that the branched alcohol in the middle region of its unsulfated chain may comprise a certain amount of the compositions of the present invention. Such materials may be present as a result of the incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with a branched alkyl sulfate surfactant in the middle region of your chain according to the present invention. M is hydrogen or a salt-forming cation depending on the synthesis method. Examples of salt-forming cations are lithium, sodium, potassium, calcium, magnesium, and quaternary alkylamines having the formula:
R3 R6- N- R4 R5 wherein R3, R (R5 and R6 are independently hydrogen, C1-C22 alkylene, branched C4-C22 alkylene, C-i-Cß alkanol, alkenylene of
C1-C22. C4-C22 branched alkenylene and mixtures thereof. The
preferred cations are ammonium (R ^, R4, R5 and R6 are equal to hydrogen), sodium, potassium, mono-, di- and trialkanolammonium, and mixtures thereof. The monoalkanolammonium compounds of the present invention have R 3 equal to C 1 -C 4 alkanol, R 4, R 5 and R 6 equal to hydrogen; the
dialkanolammonium compounds of the present invention have R 3 and R 4 equal to C 1 -C 4 alkanol, R 5 and R 6 equal to hydrogen; the compounds of
trialkanolammonium of the present invention have R3, R4 and R5 gua | to alkanol of C -CQ, R6 equal to hydrogen. Preferred alkanolammonium salts of the present invention are the mono-, di- and quaternary triammonium compounds having the formulas: H 3 N + CH 2 CH 2 OH, H 2 N + (CH 2 CH 2 OH) 2, HN + (CH 2 CH 2 OH) 3. The M that is preferred is sodium, potassium and alkanolammonium salts of C2 listed above; Sodium is more preferred. Still with respect to the previous formula, w is an integer from 0 to
13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14.
Preferred surfactant mixtures of the present invention have at least 0.001%, most preferably at least 5%, more preferably at least 20% by weight, of the mixture of one or more branched primary alkyl sulphates having the formula:
R1 R2 CH3CH2 (CH2)? CH (CH2) and CH (CH2) zOS03M
wherein the total number of carbon atoms, including branching, is from 15 to 18, and wherein also for this surfactant mixture the total average number of carbon atoms in the primary branched alkyl portions having the above formula is in the range of more than 14.5 to about 17.5; R ^ and R ^ are each independently hydrogen or C1-C3 alkyl; M is a cation soluble in water; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; as long as R ^ and R2 are not both hydrogen. More preferred are compositions having at least 5% of the mixture comprising one or more branched primary alkyl sulphates in the middle region of their chain wherein x + y equals 9 and z is at least 2. Preferably, the mixtures of surfactant comprise at least 5% of a branched primary alkyl sulfate in the middle region of its chain having R ^ and R2 independently being hydrogen, methyl, provided that R1 and R2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Most preferably, the surfactant mixtures comprise at least 20% of a branched primary alkyl sulfate in the middle region of its chain having R1 and R2 being independently hydrogen, methyl, as long as Rl and R2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. The detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of agents branched primary alkyl sulfate surfactants in the middle region of its chain, said mixture comprises at least about 5% by weight of two or more branched alkyl sulphates in the middle region of its chain having the formula:
3M
or mixtures thereof; where M represents one or more cations, a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where also when a + b = 10, a is an integer of 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13;
when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein also for this surfactant mixture, the total average number of carbon atoms in the branched primary alkyl portions having the above formulas is within the range of more than 14.5 to about 17.5. In addition, the surfactant composition of the present invention may comprise a mixture of branched primary alkyl sulphates having the formula:
R R1 R2 I I I
CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zOS03M
wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the primary branched alkyl portions having the formula above is in the range of more than 14.5 to about 17.5; R1 and R2 are each independently selected from hydrogen and C-1-C3 alkyl; as long as R,
R1 and R2 are not all hydrogen; M is a cation soluble in water; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1 and w + x + y + z is from 8 to 14; provided that when R2 is a C1-C3 alkyl the ratio of surfactants having z equal to 1 to surfactants having z of 2 or more is at least about 1: 1, preferably at least about 1: 5, most preferably at least about 1: 10 and more preferably at least about 1: 100. Also preferred are surfactant compositions wherein R2 is a Cj-C3 alkyl, comprising less than about 20%, preferably less than about 10%, most preferably less than 5% and more preferably less than 1% alkyl sulfates Branched primaries having the above formula wherein z is equal to 1. The mono-methyl branched primary alkyl sulphates are selected from the group consisting of: 3-methylpentadecanolsulfate, 4-methylpentadecanolsulfate, 5-methylpentadecanolsulfate, 6-methylpentadecanolsulfate, 7-methylpentadecanolsulfate, 8-methylpentadecanolsulfate, 9-methylpentadecanolsulfate, 10-methylpentadecanolsulfate, 11-methylpentadecanolsulfate, 12-methylpentadecanolsulfate, 13-methylpentadecanolsulfate, 3-methylhexadecanolsulfate, 4-methylhexadecanolsulfate, 5-methylhexadecanolsulfate, 6-methylhexadecanolsulfate, 7-methylhexadecanolsulfate, 8-methylhexadecanolsulfate, 9- methylhexadecanolsulfate, 10-methylhexadecanolsulfate, 11-methylhexadeca nolsulfate, 12-methylhexadecanolsulfate, 13-methylhexadecanolsulfate, 14-methylhexadecanolsulfate and mixtures thereof. The preferred di-methyl branched alkyl sulfates which are preferred are selected from the group consisting of: 2,3-methyltetradecanolsulfate, 2,4-methyltetradecanolsulfate, 2,5-methyltetradecanolsulfate, 2,6-methyltetradecanolsulfate, 2,7-methyltetradecanolsulfate, 2, 8-methyltetradecanolsulfate, 2,9-methyltetradecanolsulfate, 2,10-methyltetradecanolsulfate, 2,11-methyltetradecanolsulfate, 2,12-methyltetradecanolsulfate, 2,3-methylpentadecanolsulfate, 2,4-methylpentadecanolsulfate, 2,5-methylpentadecanolsulfate, 2,6- methylpentadecanolsulfate, 2,7-methylpentadecanolsulfate, 2,8-methylpentadecanolsulfate, 2,9-methylpentadecanolsulfate, 2,10-methylpentadecanolsulfate, 2,11-methylpentadecanolsulfate, 2,12-methylpentadecanolsulfate, 2,13-methylpentadecanolsulfate and mixtures thereof. The following branched primary alkyl sulphates comprising 16 carbon atoms and having a branching unit are examples of branched surfactants useful in the compositions of the present invention: 5-methylpentadecylsulfate having the formula:
6-methylpentadecylsulfate having the formula: 7-methylpentadecylsulfate having the formula: 8-methylpentadecylsulfate having the formula:
9-methylpentadecylsulfate having the formula:
-methylpentadecylsulfate having the formula:
s preferably sodium.
The following branched primary alkyl sulphates comprising 17 carbon atoms and having two branching units are examples of branched surfactants according to the present invention: 2,5-dimethylpentadecylsulfate having the formula:
2,6-dimethylpentadecylsulfate having the formula:
2,7-dimethylpentadecylsulfate having the formula:
2,8-dimethylpentadecylsulfate having the formula:
2,9-dimethylpentadecylsulfate having the formula: 2,10-dimethylpentadecylsulfate having the formula:
wherein M is preferably sodium.
(2) Branched primary alkyl polyoxyalipylene surfactants in the middle region of its chain The branched surfactant compositions of the present invention may comprise one or more primary alkylpolyoxyalkylene surfactants branched in the middle region of their chain having the following formula:
R R 1 R2 I
CH3CH2 (CH2) wCH (CH2)? CH (CH2) CH (CH2) z (EO / PO) mOH
The surfactant mixtures of the present invention comprise molecules having a linear primary polyoxyalkylene chain base structure (ie, the longest linear carbon chain including the alkoxylated carbon atom). These base structures of the alkyl chain comprise from 12 to 19 carbon atoms; and in addition the molecules comprise a branched primary alkyl portion having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions in the range of greater than 14.5 to about 17.5. In this manner, the blends of the present invention comprise at least one polyoxyalkylene compound having a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms The carbon including the branching must be at least 14, and furthermore the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 17.5. For example, a primary polyoxylakylene surfactant of 16 total carbons (in the alkyl chain) having 15 carbon atoms in the base structure must have a branching unit (either R, R1 or R2 is methyl) thereby the total number of carbon atoms in the molecule is at least 16. R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, most preferably hydrogen or methyl) , and more preferably methyl), as long as R, R'l and R2 are not all hydrogen. Also, when z is
1, at least R or Rl is not hydrogen. Although for the purposes of the surfactant compositions of the present invention the above formula does not include molecules in which the R, R 1 and R 2 units are all hydrogen (ie, unbranched linear primary polyoxyalkylenes), it should be recognized that the compositions of The present invention may still further comprise a certain amount of unbranched linear primary polyoxyalkylene. In addition, this unbranched linear primary polyoxyalkylene surfactant may be present as a result of the process used to make the surfactant mixture having the branched primary polyoxyalkylenes in the middle region of its chain necessary in accordance with the present invention, or for the For purposes of formulating detergent compositions, a certain amount of unbranched linear primary polyoxyalkylene can be mixed into the final product formulation. further, it should be similarly recognized that the branched alcohol in the middle region of its non-alkoxylated chain may comprise a certain amount of the polyoxyalkylene-containing compositions of the present invention. Such materials may be present as a result of the incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with a branched polyoxyalkylene surfactant in the middle region of your chain according to the present invention. Still with respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14. EO / PO are alkoxy portions, preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, most preferably ethoxy, wherein m is at least about 1, preferably in the range from about 3 to about 30, most preferably from about 5 to about 20 and more preferably from about 5 to about 15. The portion (EO / PO) m may be,
or a distribution with average degree of alkoxylation (e.g., ethoxylation and / or propoxylation) corresponding to m, or can be an individual specific chain with alkoxylation (e.g., ethoxylation and / or propoxylation) of exactly the number of units corresponding to m. The surfactant mixtures of the present invention have at least 0.001%, most preferably at least 5%, more preferably at least 20% by weight, of the mixture of one or more branched primary alkylpolyoxyalkylenes having the formula: R1 R2 II
CH3CH2 (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOH
wherein the total number of carbon atoms, including branching, is from 15 to 18, and wherein also for this surfactant mixture the total average number of carbon atoms in the primary branched alkyl portions having the above formula is on the scale of more
from 14.5 to about 17.5; R ^ and R2 are each independently hydrogen or C1-C3 alkyl; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; provided that R "and R2 are not both hydrogen, and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, most preferably ethoxy, in which m is at least about 1, preferably in the scale from about 3 to about 30, most preferably from about 5 to about 20 and more preferably from about 5 to about 15. More preferred are compositions having at least 5% of the mixture comprising one or more branched primary polyoxyalkylenes in the middle region of its chain where z is at least 2. Preferably, the surfactant mixtures comprise at least 5%, preferably at least about 20%, of a branched primary alkyl polyoxyalkylene in the middle region of its chain that has R1 and R2 being independently hydrogen or methyl, provided that R ^ and R2 are not both hydrogen, x + y is equal to 8, 9 or 10 and z is po at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a branched primary alkylpolyoxyalkylene surfactant mixture in the middle region of its chain , said mixture comprises at least about 5% by weight of one or more branched alkylpolyoxyalkylenes in the middle region of their chain having the formula:
or mixtures thereof; in which a, b, d and e are integers, a + b is 10 a
16, d + e is from 8 to 14 and in which also when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein also for this surfactant mixture, the total average number of carbon atoms in the primary branched alkyl portions having the above formulas is within the range of more than 14.5 to about 17.5; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, in
where m is at least about 1, preferably on the scale from about 3 to about 30, most preferably from
about 5 to about 20 and more preferably about 5 to about 15. In addition, the surfactant composition of the present
invention may comprise a mixture of branched primary alkyl polyoxyalkylenes having the formula:
R R1 R2 I I I
CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOH
wherein the total number of carbon atoms per molecule, including the branch, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the portions
branched primary alkyl having the above formula is on the scale
from more than 14.5 to about 17.5; R 1 and R 2 are each independently selected from hydrogen and C 1 -C 3 alkyl; as long as R,
Rl and R2 are not all hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is from 8 to 14; EO / PO are alkoxy portions preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 1, preferably in the range from about 3 to about 30, most preferably from about 5 to about 20 and more preferably from about 5 to about 15; provided that when R2 is a C1-C3 alkyl the ratio of surfactants having z equal to 2 or more to the surfactants having z of 1 is at least about 1: 1, preferably at least about 1.5: 1, most preferably at least about 3: 1 and more preferably at least about 4: 1. Also preferred are surfactant compositions wherein R2 is a C1-C3 alkyl, comprising less than about 50%, preferably less than about 40%, most preferably less than about 25% and more preferably less than about 20% , of branched primary alkyl polyoxyalkylene having the above formula wherein z is equal to 1. The mono-methyl branched primary alkyl ethoxylates are selected from the group consisting of: 3-methylpentadecanoletoxylate, 4-methylpentadecanolethoxylate, 5-methylpentadecanolethoxylate, 6-methylpentadecanolethoxylate, -metilpentadecanoletoxilato, 8-metilpentadecanoletoxilato, 9-metilpentadecanoletoxilato, 10-metilpentadecanoletoxilato, 11 metilpentadecanoletoxilato, 12-metilpentadecanoletoxilato, 13-metilpentadecanoletoxilato, 3-metilhexadecanoletoxilato, 4-metilhexadecanoletoxilato, 5-metilhexadecanoletoxilato, 6-metilhexadecanoletoxilato, metilhexadecanoletoxilato 7-, 8-metilhexadecanoletoxilato , 9-methylhexadecanoletoxylate, 10-methylhexadecanoletoxylate, 11-methylhexadecanoletoxylate, 12-methylhexadecanoletoxylate, 13-methylhexadecanoletoxylate, 14-methylhexadecanoletoxylate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of about 5 to about 15. Preferred di-methyl branched alkyl ethoxylates which are preferred are selected from the group consisting of: 2,3-methi tetradecanoletoxylate, 2,4-methyltetradecanoletoxylate, 2,5-mmeettiiltteettrraaddeeccaannoolleettooxxiillaattoo ,, 2,6-methyltetradecanoletoxilato, 2,7-meti tetradecanoletoxilato, 2,8-methyltetradecanoletoxilato, 2,9-meti tetradecanoletoxilato, 2,10-methyltetradecanol-ethoxylate, 2,11-meti tetradecanoletoxilato, 2,12-methyltetradecanoletoxilato, 2,3-meti pentadecanoletoxilato, 2,4-methylpentadecanoletoxilato, 2,5 -meti pentadecanoletoxilato, 2,6-methylpentadecanoletoxilato, 2,7-meti pentadecanoletoxilato, 2,8-methylpentadecanoletoxilato, 2,9-meti pentadecanol ethoxylate, 2,10-methylpentadecanoletoxylate, 2,11-methyl pentadecanol-ethoxylate, 2,12-methylpentadecanolethoxylate, 2,13-methyl pentadecanolethoxylate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of about 5. at about 15.
(3) Branched primary alkoxylated alkoxylated surfactant agents in the middle region of its chain The branched surfactant compositions of the present invention may comprise one or more (preferably one)
mixture of two or more) alkoxylated primary alkylsulphate surfactants branched in the middle region of their chain having the formula
R R1 R2 I I I C ^ CH ^ CH ^ CHÍCH ^ CHÍCH ^ yCHÍCH ^ ÍEO POJmO SO ^
The surfactant mixtures of the present invention comprise molecules having a linear primary alkoxylated sulfate chain base structure (ie, the longest linear carbon chain including the alkoxysulfated carbon atom). These alkyl base structures comprise from 12 to 19 carbon atoms; and in addition the molecules comprise a branched primary alkyl portion having at least a total of 14, but not more than 20, carbon atoms. Besides, the
The surfactant mixture has an average total number of carbon atoms for the branched primary alkyl portions within the range of more than 14.5 to about 17.5. In this manner, the mixtures of the present invention comprise at least one alkoxylated sulfate compound having a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of atoms of carbon including the branching must be at least 14, and in addition the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 17.5. For example, a primary alkoxylated alkylsulfate surfactant of 16 total carbons (in the alkyl chain) having 15 carbon atoms in the base structure must have a branching unit (either R, R 1 or R 2 is methyl) with which the total number of carbon atoms in the primary alkyl portion of the molecule is 16. R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, most preferably hydrogen or methyl, and more preferably methyl), provided that R, R1 and R2 are not all hydrogen. Also, when z is
1, at least R or Rl is not hydrogen. Although for the purposes of the surfactant compositions of the present invention the above formula does not include molecules in which the R, R1 and R2 units are all hydrogen (ie, unbranched linear primary alkoxylated sulfates), it should be recognized that the of the present invention may still further comprise a certain amount of unbranched linear primary alkoxylated sulfate. In addition, this unbranched linear primary alkoxylated sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the branched primary alkoxylated sulfates in the middle region of its chain necessary in accordance with the present invention, or for the purposes of formulating detergent compositions a certain amount of unbranched linear primary alkoxylated sulfate can be mixed in the final product formulation. It should also be recognized that a certain amount of branched alkyl sulfate in the middle region of its chain may be present in the compositions. This is typically the result of the sulfation of a non-alkoxylated alcohol which remains after the incomplete alkoxylation of the branched alcohol in the middle region of its chain used to prepare the alkoxylated sulfate of the present. However, it should be recognized that the separate addition of said branched alkyl sulphates in the middle region of their chain is also contemplated by the compositions of the present invention. Furthermore, it should be similarly recognized that the branched alcohol in the middle region of its unsulfated chain (including the polyoxyalkylene alcohols) may comprise a certain amount of the alkoxylated sulfate-containing compositions of the present invention. Such materials may be present as a result of the incomplete sulfation of the alcohol (alkoxylated or non-alkoxylated) used to prepare the alkoxylated sulfate surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with an alkoxylated sulfate surfactant branched in the middle region of its chain according to the present invention. M is as described above in the present.More with respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of so
Minus 1; and w + x + y + z is an integer from 8 to 14. EO / PO are alkoxy portions, preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably on the scale from about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from about 1 to about 5. The portion (EO / PO) m may be, or a distribution with
average degree of alkoxylation (e.g., ethoxylation and / or propoxylation) corresponding to m or can be an individual specific chain with alkoxylation (e.g., ethoxylation and / or propoxylation) of exactly the number of units corresponding to m . The surfactant mixtures of the present invention have at least 0.001%, most preferably at least 5%, more preferably at least 20% by weight of the mixture, of one or more branched primary alkoxylated alkyl sulfates having the formula: R1 R2 II
CH3CH2 (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mO S03M
wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein in addition for this surfactant mixture the total average number of carbon atoms in the branched primary alkyl portions having the above formula is on the scale of more than 14.5 to about 17.5; R ^ and R2 are each independently hydrogen or C1-C3 alkyl; M is a cation soluble in water; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; as long as
R1 and R2 are not both hydrogen; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably in the range from about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from about 1 to about 5. Further preferred are compositions having at least 5% of the mixture comprising one or more branched primary alkoxylated sulfates in the middle region of their chain wherein z is at least 2. preferable, the surfactant mixtures comprise at least 5%, preferably at least about 20%, of a branched primary alkoxylated alkylsulfate in the middle region of its chain having R1 and R2 independently being hydrogen or methyl, provided that R1 and R2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of branched primary alkoxylated alkyl sulfate surfactants in the middle region of its chain, said mixture comprising at least about 5% by weight of one or more branched alkoxylated alkyl sulphates in the middle region of its chain having the formula:
or mixtures thereof; where M represents one or more cations, a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where also when a + b = 10, a is an integer of 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12;
and wherein also for this surfactant mixture, the total average number of carbon atoms in the primary branched alkyl portions having the above formulas is within the range of more than 14.5 to about 17.5; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably in the range from about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from
about 1 to about 5. In addition, the surfactant composition of the present invention may comprise a mixture of branched primary alkoxylated alkyl sulfates having the formula:
R R1 R2 I I I
CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mO S03M
wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the primary branched alkyl portions having the formula previous is on the scale
from more than 14.5 to about 17.5; R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl; as long as
R, R1 and R2 are not all hydrogen; M is a cation soluble in water; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; w + x + y + z is from 8 to 14; EO / PO are alkoxy portions preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably on the scale from about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from about 1 to about 5; provided that when R2 is a C1-C3 alkyl the ratio of surfactants having z equal to 2 or more to the surfactants having z of 1 is at least about 1: 1, preferably at least about 1.5: 1, most preferably at least about
3: 1 and more preferably at least about 4: 1. Also preferred are surfactant compositions wherein R2 is a C1-C3 alkyl, comprising less than about 50%, preferably less than about 40%, most preferably less than about 25% and more preferably less than about 20% , of branched primary alkoxylated alkylsulfate having the above formula wherein z is equal to 1. The mono-methyl branched primary ethoxylated alkyl sulphates are selected from the group consisting of: 3-methylpentadecanoletoylated sulfate, 4-methylpentadecanol-ethoxylated sulfate, sulfate 5- methylpentadecanoletoylated sulphate, 6-methylpentadecanoletoylated sulfate, 7-methylpentadecanol-ethoxylated sulfate, 8-methylpentadecanoletoylated sulfate, 9-methylpentadecanoletoylated sulfate, 10-methylpentadecanol-ethoxylated sulfate, 11-methylpentadecanoletoylated sulfate, 12-methylpentadecanoletoxylated sulfate, 13-methylpentadecanol-ethoxylated sulfate, sulfate 3 -methylhexadecanoletoxilado, 4-methylhexadecanoletoxil sulfate 5-methylhexadecanoletoylated, 6-methylhexadecanoletoylated sulfate, 7-methylhexadecanol-ethoxylated sulphate, 8-methylhexadecanoletoxylated, 9-methylhexadecanoletoylated sulfate, 10-methylhexadecanol-ethoxylated sulfate, 11-methylhexadecanoletoylated sulfate, 12-methylhexadecanoletoxylated sulfate, 13-methylhexadecanol-ethoxylated sulfate , 14-methylhexadecanoletoxylated sulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about 10. The preferred di-methyl branched primary alkyl ethoxylates are selected from the group consisting of: sulfate 2,3-methyltetradecanoletoylated, 2,4-methyltetradecanoletoylated sulfate, 2,5-methyltetradecanol-ethoxylated sulfate, 2,6-methyltetradecanolethoxylated sulfate, 2,7-methyltetradecanoletoylated sulfate, 2,8-methyltetradecanol-ethoxylated sulfate, 2,9-methyltetradecanolethoxylated sulfate, 2,10-methyltetradecanolethoxylated sulfate, 2,11-methyltetradecanolethoxylated sulfate, 2,12-methyltetradecanol-ethoxylated sulfate, sulfate 2, 3-methylpentadecanoletoylated, 2,4-methylpentadecanoletoylated sulfate, 2,5-methylpentadecanol-ethoxylated sulfate, 2,6-methylpentadecanoletoylated sulfate, 2,7-methylpentadecanoletoylated sulfate, 2,8-methylpentadecanol-ethoxylated sulfate, 2,9-methylpentadecanoletoxylated sulfate, 2,10-methylpentadecanoletoxilado sulfate, 2,11-methylpentadecanoletoxilado sulfate, 2,12-methylpentadecanol-ethoxylated sulfate, 2,13-methylpentadecanoletoxila sulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of approximately 0.1 to about 10. The paste may include adjunctive surfactants such as those selected from anionics other than BAS, non-ionic, zwitterionic, ampholy and cationic classes and compatible mixtures thereof. The detergent surfactants useful herein are described in the U.S.A. 3,664,961, Norris of May 23, 1972, and in the patent of E.U.A. 3,919,678, Laughlin et al, December 30, 1975, both of which are incorporated herein by reference. Useful cationic surfactants also include those described in the U.S.A. 4,222,905, Cockrell, September 16, 1980, and in the patent of E.U.A. 4,239,659, Murphy, December 16, 1980, both of which are also incorporated herein by reference. The following are representative examples of adjunctive detergent surfactants useful in the present surfactant paste. The water-soluble salts of the higher fatty acids, ie "soaps", are also useful anionic surfactants in the present compositions. These include alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be manufactured by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and bait, ie sodium or potassium soap from tallow and coconut. Additional anionic surfactants which are suitable for use herein include the water-soluble salts, preferably alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure a straight chain alkyl group containing 10 to 20 carbon atoms and an ester group of sulfuric acid or sulfonic acid. (Included in the term "alkyl" is the alkyl portion of acyl groups). Examples of this group of synthetic surfactants are sodium and potassium alkyl sulphates, especially those obtained by sulfation of higher alcohols (Cß-iß carbon atoms) such as those produced by the reduction of glycerides of bait or coconut oil; and the sodium and potassium alkylbenzene sulphonates in which the alkyl group contains 9 to 15 carbon atoms, straight chain, for example, those of the type described in US Pat. 2,220,099 and 2,477,383. Especially valuable are linear straight-chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as Cn-13 LAS. Other anionic surfactants suitable for use herein are sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sulfonates and sulphates monoglycerides of fatty acid of coconut oil of sodium; sodium or potassium of ethylene oxide per molecule and in which the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from 1 to 10 ethylene oxide units per molecule and in which the alkyl group contains from 10 to 20 carbon atoms. In addition, suitable anionic surfactants include the water-soluble salts of alpha-sulfonated fatty acid esters containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxyalkene-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 atoms in the alkane portion; the alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; the water-soluble salts of olefin and paraffinsulfonates containing from 12 to 20 carbon atoms; beta-alkoxyalkanesulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane portion. Preferred adjunct anionic surfactants are linear alkylbenzene sulphonates of C? 0-18 and C? 0-18 alkyl sulfates. If desired, low moisture alkylsulfate paste (less than 25% water) may be the only ingredient in the surfactant agent paste. More preferred are C-io-iß alkyl sulfates, linear or branched, of either primary, secondary or tertiary. A preferred embodiment of the present invention is wherein the surfactant paste comprises from 20% to 40% of a mixture of linear sodium alkylbenzene sulfonate of C? -13 and sodium alkyl sulfate of C? 2 -16 in a ratio of 2: 1 and 1: 2. Another preferred embodiment of the detergent composition includes a mixture of C10-18 alkyl sulfate and C-? O-18 alkyl ethoxy sulfate in a weight ratio of 80:20. Non-ionic water-soluble surfactants are also useful in the instant invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be easily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Suitable nonionic surfactants include the polyethylene oxide condensates of alkylphenols, for example, the condensation products of alkylphenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or chain configuration branched, with 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in a straight or branched chain configuration, with 3 to 12 moles of ethylene oxide per mole of alcohol are included. An additional group of nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing an alkyl portion of 10 to 18 carbon atoms and 2 portions selected from the group of alkyl portions and hydroxyalkyl of 1 to 3 carbon atoms; the water-soluble phosphine oxides containing an alkyl portion of 10 to 18 atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 13 carbon atoms; and water-soluble sulfoxides containing an alkyl portion of 10 to 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of 1 to 3 carbon atoms. Preferred nonionic surfactants are of the formula R1 (OC2H4) nOH, wherein R1 is an alkyl group of C-io-C-iß or a phenyl group of C8-C-? 2 alkyl, and n is 3 to 80. Particularly preferred are the condensation products of C.sub.2 -C.sub.5 alcohols with 5 to 20 moles of ethylene oxide per mole of alcohol, for example C? 2-C? 3 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol. Additional suitable nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. The processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Pat. No. 2,965,576 and Schwartz, US patent. No. 2,703,798 the descriptions of which are incorporated herein by reference. Ampholytic surfactants include aliphatic derivatives or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic portion can be straight or branched chain and in which one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least An aliphatic substituent contains an anionic water solubilizing group. Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms. Cationic surfactants may also be included in the present invention. Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are alidides, meltyl sulfate and hydroxide. Tertiary amines may have characteristics similar to cationic surfactants at pH values in wash solution of less than 8.5. A more complete description of those and other cationic surfactants useful herein can be found in the US patent. 4,228,044, Cambre, of October 14, 1980 incorporated herein by reference. Cationic surfactants are often used in detergent compositions to provide fabric softness and / or antistatic benefits. Antistatic agents that provide some benefit of softness and which are preferred herein are the quaternary ammonium salts described in US Pat. 3,936,537, Baskerville, Jr. et al., February 3, 1976, the disclosure of which is incorporated herein by reference.
Dry starting detergent ingredients The compositions of the invention can contain all kinds of water-soluble, organic detergent components, as long as the builder material is compatible with all these materials. In addition to a detersive surfactant, at least one suitable adjunct detergent ingredient is preferably included in the detergent composition. The detergent ingredient herein is preferably selected from the group consisting of detergency builders, enzymes, bleaching agents, bleach activators, foam suppressors, soil release agents, brighteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing agents, surface cleaning agents. pH control, chelators, processing aids, crystallization aids, and mixtures thereof. The following list of detergent ingredients and mixtures thereof which may be used in the present compositions is representative of the detergent ingredients, but is not designed to be limiting. One or more detergency builders may be used in conjunction with the builder material described herein to further improve the performance of the compositions described herein. For example, the detergency builder may be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates, and mixtures thereof. The sodium carbonate ingredient can serve as the inorganic alkaline material when a liquid acid precursor of the branched surfactant in the middle region of its chain is used. Other suitable auxiliary detergency builders are described below. Preferred builders include aluminosilicate and sodium carbonate exchange materials. The aluminosilicate ion exchange materials used herein as a detergent builder preferably have a high calcium ion exchange capacity and a high exchange rate. Without wishing to be bound by theory, it is believed that said high velocity and calcium ion exchange capacity are a function of several interrelated factors that are derived from the method by which the aluminosilicate ion exchange material is produced. In this regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al., U.S. Patent No. 4,605,509 (Procter &Gamble), the disclosure of which is incorporated herein by reference. by reference. Preferably, the aluminosilicate ion exchange material is in the "sodium" form because the potassium and hydrogen forms of the aluminosilicate at the time do not exhibit the exchange rate and capacity as high as that provided by the sodium form. Additionally, the aluminosilicate ion exchange material is preferably in dry form so as to facilitate the production of brittle detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters that optimize their effectiveness as detergent builders. The term "particle size diameter" as used herein represents the average particle size diameter of an aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and electron scanning microscope. (SEM). The preferred particle size diameter of the aluminosilicate is from 1 micron to 10 microns, more preferably from 5 microns to 9 microns. More preferably, the particle size diameter is from 1 micron to 8 microns. Preferably, the aluminosilicate ion exchange material has the formula:
Naz [(AI02) z. (Si02) and] xH20 In which z and e are integers of at least 6, the molar ratio of zay is from 1 to 5 and x is from 10 to 264. More preferably, the aluminosilicate has the formula: Na12 [(AIO2) 12. (SiO2) 12] xH2O Where x is from 20 to 30, preferably about 27. Those preferred aluminosislicates are commercially available, for example under the designations Zeolite A, Zeolite B and Zeolite X. Alternatively, the naturally occurring aluminosilicate ion exchange materials or synthetic derivatives for use herein may be manufactured as described in Krummel et al., U.S. Patent No. 3,895,669, the disclosure of which is incorporated herein by reference. the present by reference. The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least 200 mg hardness equivalents / gram of CaC 3, calculated on an anhydrous basis which is preferably on a scale of 300 to 352 mg hardness / gram equivalents of CaCÜ3. Additionally, the aluminosilicate ion exchange materials of the moment are further characterized by their calcium ion exchange rate which is at least 2 grains Ca ++ / 3.745 liters / minute / -gmo / 3.745 liters, and more preferably in one scale of approximately 2 grains Ca ++ / 3.745 liters / minute / -gram / 3.745 liters to approximately 6 grains Ca ++ / 3.745 liters / minute / -gram / 3.745 liters.
In order to make the present invention more easily understandable, reference is made to the following examples, which are designed to be illustrative only and are not designed to be limiting in scope.
EXAMPLE I
This example illustrates the process of the invention which produces high density, brittle, free flowing detergent composition. Two feed streams of various starting detergent ingredients are fed continuously, at a rate of 2800 kg / hr into a Lódige CB-30 mixer / densifier, one of which comprises a surfactant paste containing surfactant and water and the other stream contains dry starting detergent material containing aluminosilicate and sodium carbonate. The rotational speed of the shaft in the Lódige CB-30 mixer / densifier is approximately 1400 rpm and the average residence time is approximately 10 seconds. The contents of the Lódige mixer / densifier CB-30 are fed continuously into a mixer / densifier Lódige KM 600 for further agglomeration during which the average residence time is approximately 30 seconds. The resulting detergent agglomerates are then fed to a fluid bed dryer and then to a fluid bed cooler, the average residence time being from 10 minutes to 15 minutes, respectively. A coating agent, aluminosilicate, is then fed to the mixer / densifier Lódige KM 600 to control and prevent over agglomeration. The detergent agglomerates are then screened with conventional screening apparatus resulting in a uniform particle size distribution. The composition of the detergent agglomerates that come out of the fluid bed cooler for three runs of procedures are shown in Table 1 below:
TABLE 1
Component Percentage by weight of the total supplied A B C C16.5BAS 40.0 46.0 31.0
Aluminosilicate 25.4 24.0 24.0 Sodium carbonate 26.3 24.0 24.0 Polyethylene glycol (MW 4000) 1.1 1.7 2.0 Miscellaneous (water, etc.) 6A to 5 100.0 100.0 100.0
Additional detergent ingredients, including perfumes, enzymes, and other minor ones are sprayed onto the agglomerates described above in the finishing step to result in a finished detergent composition. The relative proportions of the total finished detergent composition produced by the process procedure of the moment are presented in Table II below.
TABLE 2
Component (percentage by weight) r ?? C16.5BAS, C14-15AS and C12.3LAS1 39.8 Neodol 23-e.s2 3.0 N-methyl glucamide from C? 2- 0.9 Polyacrylate (MW = 4500) 3.0 Polyethylene glycol (MW = 4000) 1.2 Sodium sulphate 8.9
Aluminosilicate 2.8 Sodium carbonate 27.2 Protease enzyme 0.4 Enzyme amylase 0.1 Enzyme lipase 0.2 Enzyme cellulase 0.1 Minor (water, perfume, etc.) 12.4 100.0
1 A mixture of C16.5 alkyl sulfate surfactants ("BAS") branched in the middle part of its chain, C-alkyl sulfate. -? 5 and linear alkylbenzene sulfonate ("AS") of C12-? 3. 2 Alkyl ethoxylate of C? 2-13 (EO = 6.5) commercially available from Shell Oil Company. The density of the resulting detergent composition is 796 g / l, the average particle size is 613 microns.
EXAMPLE ll-lll
Various detergent compositions made according to the invention and specifically for top loading washing machines are illustrated below. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed in a slurry and passed through a spray-drying tower having a counterflow current of hot air ( 200-300 ° C) resulting in the formation of porous granules. The mixed agglomerates are formed from 2 feed streams of several starting detergent ingredients that are fed continuously, at a rate of 1400 kg / hr into a Lódige mixer / densifier CB-30, one of which comprises an agent paste. surfactant containing surfactant and water and the other stream contains dry starting detergent material containing aluminosilicate and sodium carbonate. The rotational speed of the shaft in the Lódige CB-30 mixer / densifier is approximately 1400 rpm and the average residence time is approximately 5-10 seconds. The contents of the Lódige mixer / densifier CB-30 are fed continuously into a mixer / densifier Lódige KM 600 for further agglomeration during which the average residence time is approximately 1-2 minutes. The resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being mixed with the spray dried granules. The remaining detergent ingredients are sprayed on or added dry to the mixture of agglomerates and granules.
1. - Diethylenetriaminepentaacetic acid 2.- Manufactured according to US Pat. No. 5,415,807 of May 16, 1995 to Gosselink et al. 3.- Nonanoiloxybenzenesulfonate 4.- Acquired from Novo Nordisk A / S 5.- Acquired from Genencor 6.- Acquired from Ciba-Geigy Having described the invention in detail in this way, it will be clear to those skilled in the art that they can be made several changes without departing from the scope of the invention and the invention should not be considered limited to what is described in the specification.
Claims (16)
1. - A method for continuously preparing a high density detergent composition comprising the steps of: (A) continuously mixing a paste of surfactant and dry starting detergent material in a mixer / densifier at high speed to obtain detergent agglomerates, characterized in that the ratio of said surfactant paste to the dry detergent material is from 1: 10 to 10: 1, said surfactant paste contains branched surfactant compounds in the middle region of its chain of the formula: Ab-X-B wherein a) Ab is a branched alkyl portion in the middle region of the chain, hydrophobic from C9 to C22, total carbons in the portion, preferably from about C12 to C18, having: 1) a longer linear carbon chain attached to the -XB portion on a scale of 8 to 21 carbon atoms; 2) one or more C1-C3 alkyl portions branching from this longest linear carbon chain; 3) at least one of the branching alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon 2 position scale, counting from the # 1 carbon that joins the -XB portion to the carbon position -2, the terminal carbon minus 2 carbons; and 4) the surfactant composition has an average total number of carbon atoms in the Ab-X portion in the above formula within the range of more than 14.5 to about 18; b) B is a hydrophilic portion selected from sulfates, sulphonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinatamines, polyalkoxylated carboxylates, glucamides, taurinates , sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycerol ether sulphates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkenesulfonates, amidopropylbetaines, alkylated quaternary compounds, alkylated / polyhydroxyalkylated quaternary compounds, alkylated quaternary compounds, alkylated / polyhydroxylated oxopropyl quaternary compounds, imidazolines, 2-yl succinates, alkyl esters sulphonated and sulfonated fatty acids; and c) X is -CH2-; (B) mixing said detergent agglomerates in a mixer / agglomerator at moderate speed to further densify and agglomerate said detergent agglomerates; and (C) drying said detergent agglomerates to form said high density detergent composition.
2. A process according to claim 1 further characterized in that the portion Ab is a branched primary alkyl portion having the formula: R R1 R2 C ^ CH ^ CH ^ CHYCH ^ CHYCH ^ C CH ^ - in which the total number of carbon atoms in the primary alkyl moiety branched of this formula, including the branching of R, R1 and R2, is 13 to 19; R, R ^ and R2 are each independently selected from hydrogen and C1-C3 alkyl, preferably methyl, with the proviso that R, R1 and R2 are not all hydrogen and, when z is 0, at least R or R1 is not hydrogen; w is an integer from 0 to 13, x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 1
3. 3. A process according to claim 1 further characterized in that the Ab portion is a branched primary alkyl portion having the formula selected from: or mixtures thereof; in which a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and in which also when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and is an integer from 1 to 12.
4. A method according to claim 1 further characterized in that the dry starting detergent material is selected from the group consisting of aluminosilicates, crystalline layered silicates, sodium carbonate and mixtures thereof.
5. A process according to claim 1 further comprising the step of extruding the surfactant paste into an extruder before step (A).
6. A method according to claim 1 further comprising the step of adding a coating agent after the moderate speed mixer / densifier.
7. A process according to claim 6 further characterized in that the coating agent is selected from the group consisting of aluminosilicates, carbonates, silicates, builder material, and mixtures thereof.
8. A method according to claim 1 further characterized in that the ratio of surfactant paste to said starting detergent material is from 1: 4 to 4: 1.
9. A process according to claim 1 further characterized in that the surfactant paste has a viscosity of 5,000 cps to 450,000 cps and additionally comprises water and adjunctive surfactant selected from the group consisting of nonionic, zwitterionic, ampholytic surfactants , and cationic and mixtures thereof.
10. A process for continuously preparing a high density detergent composition comprising the steps of: (A) spray drying an aqueous suspension containing a branched surfactant in the middle part of its chain and attached detergent ingredients to form dried granules by spray, further characterized in that said branched surfactant in the middle part of its chain has the formula: A - X - B wherein a) Ab is a branched alkyl portion in the middle region of the chain, hydrophobic from Cg to C22 . total carbons in the portion, preferably from about C12 to C18, having: 1) a longer linear carbon chain attached to the -X-B portion on the scale of 8 to 21 carbon atoms; 2) one or more C1-C3 alkyl portions branching from this longest linear carbon chain; 3) at least one of the branching alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon 2 position scale, counting from the # 1 carbon that joins the -XB portion to the carbon position? -2, the terminal carbon minus 2 carbons; and 4) the surfactant composition has an average total number of carbon atoms in the Ab-X portion in the above formula within the range of more than 14.5 to about 18; b) B is a hydrophilic portion selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinatamines, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycerol ether sulphates, sorbitan esters, sorbitan esters polyalkoxylates, ammonium alkenesulfonates, amidopropyl betaines, alkylated quaternary compounds, alkylated / polyhydroxyalkylated quaternary compounds, alkylated quaternary compounds, alkylated / polyhydroxylated oxopropyl quaternary compounds, imidazolines, 2-yl succinates, sulfonated alkyl esters and sulfonated fatty acids; and c) X is -CH2-; (B) continuously mixing a paste of detergent surfactant and dry detergent starting material in a moderate high speed mixer / agglomerator to obtain detergent agglomerates, characterized in that the ratio of said surfactant paste to said dry detergent material is 1: 10 to 10: 1; and (C) mixing said detergent agglomerates in a mixer / densifier at moderate speed to further densify and agglomerate said detergent agglomerates; and (D) mixing the granules and the detergent agglomerates together to form the high density detergent composition.
11. A process for continuously preparing a high density detergent composition comprising the steps of: (A) continuously mixing an acid precursor of an anionic surfactant and dry starting detergent material containing an alkaline inorganic material capable of neutralizing said acid precursor in a high-speed mixer / densifier to obtain detergent agglomerates, further characterized in that the ratio of said surfactant paste to the dry detergent material is from 1: 10 to 10: 1, said surfactant paste contains branched surfactant in the middle region of its chain of the formula: Ab-X-B wherein a) Ab is a branched alkyl portion in the middle region of the chain, hydrophobic from C9 to C22, total carbons in the portion, preferably from about C12 to C18, which has: 1) a longer linear carbon chain attached to the -XB portion on a scale of 8 to 21 ato carbon 2) one or more C1-C3 alkyl portions branching from this longest linear carbon chain; 3) at least one of the branching alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon 2 position scale, counting from the # 1 carbon that joins the -XB portion to the carbon position? -2, the terminal carbon minus 2 carbons; and 4) the surfactant composition has an average total number of carbon atoms in the Ab-X portion in the above formula within the range of more than 14.5 to about 18; b) B is a hydrophilic portion selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinatamines, polyalkoxylated carboxylates, glucamides, taurinates , sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycerol ether sulphates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkenesulfonates, amidopropylbetaines, alkylated quaternary compounds, alkylated / polyhydroxyalkylated quaternary compounds, alkylated quaternary compounds, alkylated / polyhydroxylated oxopropyl quaternary compounds, imidazolines, 2-yl succinates, alkyl esters sulfonated cos and sulfonated fatty acids; and c) X is -CH2-; (B) mixing said detergent agglomerates in a mixer / agglomerator at moderate speed to further densify and agglomerate said detergent agglomerates; and (C) drying said detergent agglomerates to form said high density detergent composition.
12. A process according to claim 1 further characterized in that the Ab portion is a branched primary alkyl portion having the formula: R R1. R2 wherein the total number of carbon atoms in the branched primary alkyl portion of this formula, including the branching of R, R1 and R2, is from 13 to 19; R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl, preferably methyl, with the proviso that R, R1 and R2 are not all hydrogen and, when z is 0, at least R or R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to
13. 13. A process according to claim 1 further characterized in that the Ab portion is a primary branched alkyl portion having the formula selected from: CH (I) CH3 (CH2) aCH (CH2) b- > or mixtures thereof; in which a, b, d and e are integers, a + b is 10 a 16, d + e is from 8 to 14 and in which also when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer of 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and is an integer from 1 to 12.
14. A high-density detergent product manufactured in accordance with claim 1, further characterized in that said product comprises agglomerates containing from 20% to 50% by weight of branched surfactant in the middle region of its chain, from 10% to 65% of a detergent builder, and up to 40% by weight of sodium carbonate.
15. A high-density detergent product manufactured in accordance with claim 10.
16. A high-density detergent product manufactured in accordance with claim 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/061,876 | 1997-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA00003520A true MXPA00003520A (en) | 2001-12-04 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5496487A (en) | Agglomeration process for making a detergent composition utilizing existing spray drying towers for conditioning detergent agglomerates | |
| MXPA97002099A (en) | Procedure to make a high density detergent composition that includes recirculation currents select | |
| JPH06100899A (en) | Detergent composition | |
| CA2305278C (en) | Detergent-making process using a high active surfactant paste containing mid-chain branched surfactants | |
| CA2296553C (en) | Process for making a low density detergent composition by controlling agglomeration via particle size | |
| WO1995032276A1 (en) | Process for making a high density detergent composition from starting detergent ingredients | |
| CA2305351A1 (en) | Process for making a high density granular detergent composition containing mid-chain branched surfactants | |
| CA2305324C (en) | Processes for making a granular detergent composition containing mid-chain branched surfactants | |
| EP1505147A1 (en) | Process for producing granular anionic surfactant | |
| EP1005522B1 (en) | Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer | |
| JPH0762160B2 (en) | Process for producing high bulk density detergent powder containing clay | |
| WO1998014550A1 (en) | Process for making a low density detergent composition | |
| MXPA00003520A (en) | Processes for making a granular detergent composition containing mid-chain branched surfactants | |
| EP1141197B1 (en) | Processes for making a granular detergent composition containing modified carboxy methyl cellulose | |
| CA2362413A1 (en) | Process for producing coated detergent particles | |
| US6576605B1 (en) | Process for making a free flowing detergent composition | |
| US6281188B1 (en) | Process for making a low density detergent composition | |
| MXPA00003515A (en) | Process for making a high density granular detergent composition containing mid-chain branched surfactants | |
| US6440342B1 (en) | Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer | |
| US6248709B1 (en) | Process for making a detergent composition by adding co-surfactants | |
| US6156719A (en) | Process for making a low density detergent composition by non-tower process | |
| EP1115837B1 (en) | Granular detergent compositions having homogenous particles and process for producing same | |
| MXPA00003527A (en) | Detergent-making process using a high active surfactant paste containing mid-chain branched surfactants | |
| MXPA96005754A (en) | Procedure for the manufacture of a high-density detergent composition from detergent ingredients | |
| WO2000024861A1 (en) | Process for making a free flowing detergent composition |